The Three Lions only needed a point against the Azzurri to guarantee themselves of a spot in next year's tournament in Germany, but managed to take all three.
But they started in the worst possible fashion in front of their own fans as ex-West Ham striker Gianluca Scamacca broke the deadlock in the 15th minute.
Making his first appearance in England since being sold to Atalanta in the summer, the 24-year-old fired home from close range to silence the supporters.
However the visitors' lead didn't last long, as skipper Harry Kane notched up his 60th international goal just after the half-hour mark.
The Bayern Munich marksman dispatched a penalty into the top right corner after Jude Bellingham was brought down by Giovanni Di Lorenzo.
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And just 12 minutes after the break, Marcus Rashford fired home into the bottom right corner, with Bellingham again the architect.
Kane then scored his second of the night in the 77th minute as he coolly slotted past the onrushing Gianluigi Donnarumma.
It means that England have won Group C with two matches to spare, and have the luxury of rotating their line-up for next month's clashes against Malta and North Macedonia.
England have also done the double over Italy, with Gareth Southgate's men getting Wembley revenge over Luciano Spalletti's side.
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It was just over two years ago that Italy beat England on penalties at the Home of Football in the Euro 2020 final.
Southgate's star-studded squad will be looking to go one better next time in Germany in their quest to win a first European Championship.
As for Italy, they sit third in Group C - three points behind second-placed Ukraine - though they have played a game less.